clean fuel and petrochemicals
TRANSCRIPT
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Clean FuelsandPetrochemical SynergiesLecture
Advanced Training CourseOn Clean Fuels
Indian Institute of Petroleum, IndiaDr. A. K. Gupta
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Returns on refining assets fallen to
inadequate levels due to
- Low growth for major refined products
- Poor upgrading margins
- Increased competition
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The drivers to these issues are:
Refinery/ Petrochemical Integration
Business diversification challenges (e.g.power generation, retail marketing)
Process technology developments Regulatory issues
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Growth Rate
Global Petroleum demand isexpected to average 2.2% duringnext 10 years
Global demand for majorpetrochemical will grow twice asfast.
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All the major petrochemical producing regions will be addingpetrochemical processing capacity to 2005
Petrochemical New Investment/additionMillion tons/ year
Ethylene 41.3
Benzene 10.5
Styrene 11.4
Poly-olefins+ 50.1
Para-xylene (PX) 11.1
Terephthalic Acid (PTA) 15.5
+ Polyolefins includes polypropylene, all grades of polyethylene(including LDPE- 29.2 million tons/year, LLDPE- 20.9 million
tons/year and HDPE
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WORLD ETHYLENE CAPACITY (MAY 1997)
1997 2000 % increase from 1997 to
2000North America 28,732 31,619 10
South America 3365 3935 16.9
West Europe 19,786 20,046 1.3
East Europe 7568 8058 6.5
Africa 1255 1555 23.9
Middle East 4846 6611 36.4
Asia 17812 22573 26.7
Australia 505 505 -
TOTAL 83,869 94,902 13.2
Source: Japan Petrochemical Industry Association, Tokyo, May 1997
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Propylene demand continues to exceedgrowth in production from steamcrackers
Projects to produce additionalpropylene from Refinery FCC units arebeing considered.
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ASIAN ETHYLENE PRODUCTION CAPACITY
1991 1997 2000* 2005/10*
Japan 6150 7114 7478 8554
South Korea 1232 3720 4380 4380China 2225 2338 4205 6723
Taiwan 745 960 1390 2365
East Asia Total 10,352 14,132 17,453 22,472
Singapore 400 960 1005 1760Thailand 230 1130 1130 1730
Malaysia - 530 1010 1600
Indonesia - 550 715 2265
Philippines - - - 500Asean Total 630 3170 3860 7855
India 510 510 1260 3950
Asia Grand Total 11,492 17,812 22,573 34,277
*Few of the above planned projects may not materialize or may be postponed, especiallythose in China and India.
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World-scale steam cracker facilities
under construction cannot keep up withdemand
Result-
Refinery- based petrochemicals can
play a significant role in providing asecurity of supply to petrochemicalprocessors
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INDIAN SCENE.
Post Administered Pricing Regime (APR)- Allow world market prices for refined products to be applied in India
As product prices change, the refineries will be faced with the need toimprove allocation of their capital and optimize crude oil selection
strategies. The products most in demand will be transportation fuels- diesel and
motor, meeting the stringent environmental regulations
Capacity increase and meeting specifications of fuels to meet stringent
regulations will be involve huge capital investments
Refinery profits will squeeze
Alternative options to improve profitability need to be looked into
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Profitability Cycles
Petrochemicals often exhibit cyclical profitability(6-7 years cycles)
Refining industry, cyclically differs in both timingand severity compared to petrochemicals
- Integration allows to temper the downturnsin petrochemicals by the more stable behaviorof refining cycle.
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Refinery/ Petrochemical integration also
brings other synergistic opportunities
- Energy optimization and cogeneration
- Recycling H2 from integratedpetrochemical complexes to refinery forincreased demand in hydroprocessingin reformulated products.
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Benefits of Integration
Advantage of Counter-seasonal trends in fuel/transportdemand vs. Petrochemical feedstock requirements.
Integrated economics often reflect lower refinery values forpetrochemical feed-stocks.
Many big products from the petrochemical operations can berecycled back to the refinery at higher value.
Competitive edge over stand-alone petrochemical complexes
Overall economics also improves from shared utilities,transportation, maintenance and administrative functions.
Finally, petrochemicals generally offer higher value, bettergrowth opportunities.
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Obstacles that can deter investments in
extending refinery operations into petro-
chemical operations include: High capital costs of new petrochemical units
Product/intermediate transfer costs betweenrefinery and petrochemical divisions
Refiners may see a higher rate of return in other
business such as retail marketing In contrast to refiners, many chemical industry
players prefer to make smaller acquisitions to fit
existing portfolios and minimize risks
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The future of petrochemical integrationinto the refinery cannot be characterizedin simple terms. It must first be
recognized that petrochemical industry isa large industry with many products and
more than 500 processes.
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If an existing refining facility does notalready produce a sizable quantity ofpetrochemical products, can it ever
hope to achieve an acceptable returnon petrochemical projects?
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Refiners produce a wide range of chemicalfeedstocks depending on crude type, refinerycomplexity, and other operating conditions.
Typically a limited number of refineryprocesses/ streams provide the primaryfeedstocks to support competitively sizedpetrochemical production.
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Contd..
PETROCHEMICALS FROM REFINERY STREAMS
Petrochemical Stream Refinery Stream Alternative
Refinery Use
Base PetrochemicalsEthylene Naphtha and LPG Fuel gas
Propylene Refinery propylene (FCC product) Alkylation
Benzene, toluene, xylenes(BTX)
Reformate Gasolineblending
Downstream Derivatives
Ethylbenzene Dilute ethylene (FCC and delayedcoker off-gases)
Fuel gas
Polypropylene Refinery propylene (FCC product) Alkylation
Isopropanol Refinery propylene (FCC product) Alkylation
Cumene Refinery propylene (FCC product) Alkylation
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Oligomers Refinery propylene
(FCC and delayed coker)
Alkylation
MEK Butylenes
(FCC and delayed coker)
Alkylation, MTBE Production
MTBE Butylenes
(FCC and delayed coker)
Alkylation, MTBE Production
Cyclohexane Reformate Gasoline blending
Ortho-Xylene Reformate Gasoline blending
Para-Xylene Reformate Gasoline blending
Normal paraffins Kerosene Refinery product
Naphthalene FCC light cycle oil Diesel blend-stock after
hydro-treating
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Contd.
REFINERY-GENERATED FEED-STOCKS AND THEIR COMMONAND POTENTIAL USAGE
Feed-Stock Derivatives
LPG (Propane,Butane)
Feedstock for:
Ethylene, Propylene, Butylenes by steamcracking/dehydrogenation:
Aromatics by aromizing
Acid, aldehydes & ketones through oxidn.
Naphtha Light and heavy for olefins and aromatics production,depending upon the composition (steamcracking/Reforming)
Light naphtha to C5-stream
Hydrogenation of benzene rich fraction (69-90C) forcyclohexane/ cyclohexene, which is feed stock forfibre industry.
Kerosene n-paraffins for LAB, LAS etc.
specialty chemicals, plasticizers and solvent
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Contd.
Gas Oil Feedstock for steam cracking to produce olefins(commonly used in china).
Gas oil from thermal conversion process- alpha
olefins for AOS.FCC off gases Propylene, isopropanol, cumene, oligomers,
polypropylene, acrylic acid.
Butylenes- MEK, MTBE, oligomers, purebutene-1, alkyl phenols and additives, acrolein,
MMA acrylic acid.
High octane, benzene free gasoline blendingcomponent by alkylating benzene rich naphthawith FCC- off gases and isobutene.
DCC
Olefins
Kerosene fromthermal process(visbreaking, coking)
n-paraffins, alpha olefins,
aromatics naphthalene
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Reformate BTX
C9+ aromatics from reformate and their
conversion,
Residues sludge,coke etc.
Power (IGCC), steam, H2, Syn gas-chemicals,High cetane, zero sulfur diesel, specialty linearwaxes, olefins, alcohols etc.
Petroleum Coke Use based on acetylene chemistry
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Levels of Refining and Petrochemical
Integrations
Forward Integration
Utilization of refinery manufactured products aspetrochemical feedstock rather than gasolineblending component.
Backward Integration Disposal of petrochemical by-products to
refinery applications, namely gasoline blending.
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Site-wide and System-wide Integration
Side-wide integration
Petrochemical and refining operations areintegrated on one site.
System-wide integration
Products are traded between severalindependent refinery and petrochemicalsites.
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Figure 1: process Flow diagram of an integrated refinery & Petrochemicals plant
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Basic Petrochemical Plans
1. Steam cracker or olefins plant.
2. Aromatic Plant
Both units obtain feedstocks from refining section.
LPG, light or full range naphtha and unconvertedoil for steam cracker.
Reformate for aromatics.
Alternatively these feedstocks are also availablefrom the market.
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Alternatives for light naphtha
1. Feedstock for steam cracker
2. Feed stock for isomerisation unit
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Alternatives for Reformate
1. Feedstock for Aromatics
2. Gasoline Blending Component
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Auto Oil Programmes will
Affect
Recipe for gasoline blending
Choice for feedstocks for steam cracking
and aromatics unit.
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Both steam crackers and aromatics
units
Produce by-products in addition to C2H4,C3H6 or aromatics.
Some of these by-products return to therefinery as gasoline blend stocks calledChemical Returns.
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Changing fuel specifications will have animpact on the interfaces or synergies of
refining and petrochemical operations.
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Chemical returns from steam cracker
include : pyrolysis gasoline, followingbenzene extraction
Pygas split - Light & heavy
Chemical returns from aromatic unit consistsof C9 or C8 (xylenes) aromatics.
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The fuel regulations being enacted will
change the blending values andopportunities for chemical returns as well asthe availability of light naphtha as cracker
feed.
This effect will be increased by the fact that
gasoline demand is expected to increase atlow pace than demand for C2H4 and C3H6.
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Gasoline Specification due to AOP
Before AOP AOP 200 AOP 2005
Sulphur ppm Max. 500 Max. 150 Max. 50
Benzene %v/v Max. 5 Max. 1 Max. 1
Aromatics %v/v - Max. 42 Max. 35
Olefins %v/v - Max. 18 Max. 18
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Changing Gasoline Specifications
Sulfur
Benzene
Aromatics
Olefins
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Impact of Changing Gasoline
Specifications
The changing Gasoline specifications will influence:
Quantity and quality of feed stocks available forpetrochemical production.
Gasoline blending strategies.
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The reduction in aromatics content of
gasoline will have major impact on refining-petrochemical synergies.
All other parameters also needs to beconsidered; these will limit the blendingreturns into gasoline pool and restrict the
availability of light naphtha as petrochemicalfeedstock.
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There are four general refinery types
Hydroskimmer, refineries consisting only of topping andreforming.
FCC-type, refineries with FCC plant for VGO or rasid
cracking without additional hydrogen.
Hydrocracker type, refineries including a hydrocracker plantfor VGO cracking with hydrogen addition.
Complex or FCC/Hydrocracker type, are refineries withboth types of cracking units.
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Refinery types and aromatics content in gasoline
HydroskimmerTopping and Reforming units only
About 51% aromatics content in gasoline; corresponding to 77% reformate
FCC type
Hydroskimming and additional FCC for VGO cracking without hydrogen additionless than 35% aromatics content in gasoline; corresponding to about 38% reformate
Hydrocracker type
Hydroskimming and additional Hydrocracker for VGO cracking with hydrogen
addition about 54% aromatics content in gasoline; corresponding to 83% reformate.Complex or FCC/HC type
Hydroskimming plus FCC and HC units
About 45% aromatics content in gasoline; corresponding to 60% reformate
Q li i f i l li bl di
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Qualities of typical gasoline blending components
Blending
Component
Benzene
Vol%
Sulphur
ppm
Olefins
vol%
Aromatics
Vol%
RON/MON
Reformate 1,0-10 1 0 60-75 99/98
FCC gasoline 0,7-1,0 100-2000 30-40 5-45 91-96 / 78-84
-light cut 0,9-1,5 15-300 20-55 1-2 98-96/80-82
-heavy cut 0,1-1,1 350-3500 2-14 40-60 91-96/78-84
Isomerisate 0 0 0 0 87-92/84-90
Alkylate 0 0 1 0 95/93
MTBE 0 0 1 0 111/96
Pyrolysisgasoline
0-6 0-600 25-35 75-88 98/84
- light cut 0-6 0-50 55 5 96/80
-heavy cut
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Blend Stock Qualities
Pyrolysis Gasoline quality parameters are similar toFCC gasoline.
PG has favourable RON and acceptable MON.
Sulfur, olefins and aromatics content of PG exceedfuture gasoline specs.
Light PG is low in aromatics but olefins content isextremely high; MON is insufficient.
Reverse is true for heavy PG high aromatics low
olefins.
Pyrolysis Gasoline (PG)
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C-9 Aromatics
C-9 aromatics are excellent gasoline blendstock
High aromaticity. Negligible olefin content.
Octane comparable to reformate
High aromaticity will limit the future usageas blends.
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Reformate has added advantages over C-9
aromatics
Reformate has lower aromatic content.
Naphtha reforming generates H2 as by-product.
Distillation range of reformate favourable to gasolineblending.
C9-aromatics production can be reduced by cuttingreformer feed TBP (140C max.)
One option to limit aromatics in gasoline is dilution
with MTBE, alkylate, isomerisate etc.
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Due to high aromatics and olefinscontent chemical returns used asgasoline blending components is likely to
provide less revenues
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At 42% aromatics level:
As gasoline blends Hydroskimmer andHydrocracker refineries are limited by aromatics
specifications.
Sulfur is constraint for FCC and complex
refineries
FCC gasoline blending is not limited byaromatics content.
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At 35% aromatic limitation:
FCC refineries will not be able to take aromaticssurplus-refineries or C9-aromatics from
petrochemical operations.
Solution lies in dilution
- isomerisate
- Extraction of aromatics
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The reasons for increasing the isomeratecapacity may be summarized as follows:
Easy availability of light naphtha,
Increasing gasoline demand,
Lead phase-out,
Regular grade versus Euro Super and Super 98,
Benzene limitation,
Aromatics limitation,
Sulphur limitation, as the octane losses of FCClight gasoline due to deep hydrogenation have tobe compensated.
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Steam Cracker feed stock
Increasing use of isomerisation will affect steamcracker feed supply and quality.
Unconverted oil (UCO) form hydrocrackerproduces less ethylene than high quality naphtha.
Ethane and LPG are other alternatives.
Condensate may emerge as real alternative.
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Naphtha volume and quality will
change due to:
Increasing light naphtha/isomerate
requirements at refinery site for aromaticsdilution.
And because of growing olefins demand whilefuel requirements are stable or relaxed.
Ch i hth lit
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Changing naphtha quality:
will cause lower ethylene and propylene yields at the same
throughput, while pygas output will increase.
changing naphtha quality will also cause higher aromaticscontent in pygas and larger heavy pygas volumes.
due to more stringent gasoline specifications especially withrespect to aromatics.
there will be lower blending values of pygas and C9-
aromatics.
and a limiting of light pygas blending into gasoline due tohigh olefin content.
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Synergies between FCC and olefin
production
Catalytic Cracking can be a supplementarysource for olefins.
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Generally FCC is designed to produce gasoline anddiesel. (Large pore zeolites)
Medium pore zeolites over crack gasoline to propyleneand butylenes
- Pentasil family of molecular sieves are
used for this application- ZSM-5 structure most successful
- Product gases contain 5-7 wt% propylene
OLEFINS FROM FCC
DEEP CATALYTIC CRACKING (DCC)
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DEEP CATALYTIC CRACKING (DCC)
DCC is an extension of FCC process to producemore propylene and butylenes.
Propylene yields of 18-20% can be obtained
Modes of operation
- maximization of propylene
- maximization of iso-olefins Overall scheme is very similar to that of a
conventional FCC
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Typical Operation Conditions
DCC FCC Steam
Cracking
Temperature C 1020-1100 920-1020 1400-1600
Cat./oil ratio 8-15 4-10 --
Dispersionsteam wt%
10-30 0-2 30-80
Pressure, psig 15-30 15-30 atm
Petro FCC
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Petro FCC
Targets producing petrochemical feedstocks rather than fuel
products
Based on new catalyst (Rx-Cat) to improve yield of propyleneand aromatics.
- Lower HC partial pressure
- Slightly higher reactor outlet temperature
- Improved spent catalyst stripping- Nearly eliminating post-riser, non-selective back-mixed
cracking
- High catalyst flux rates
Yi ld P tt
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Yield Patterns
Component, wt% Traditional FCC Petro FCC
H2S, H2, C1 & C2Ethylene
Propane
Propylene
Butanes
Butylenes
Naphtha
DistillateFuel Oil
Coke
2.0
1.0
1.8
4.7
4.5
6.5
53.5
14.07.0
5.0
3.0
6.0
2.0
22.0
5.0
14.0
28.0
9.55.0
5.5
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Catalytic Pyrolysis Process (CPP)
It is a hybrid DCC- steam crackingsystem.
Operated under more severe conditionsthan DCC
Combined yield of C2-C4 is very high It is a petrochemical process designed tomake a range of olefins and aromatics.
CATALYTIC PYROLYSIS PROCESS TYPICAL
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CATALYTIC PYROLYSIS PROCESS- TYPICAL
PRODUCT DISTRIBUTION
Product yield, wt%
Ethylene 22.78
Propylene & butylene 29.62C5+ naphtha 14.93
LCO 3.72
HCO 4.56
Coke 8.67
Conversion, wt% 91.72
(Feed: atm residue)
RESID PROCESSING
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RESID PROCESSING
Currently the primary goal of an Indian refinery is: To upgrade as much crude as possible into saleable fuel products.
Maximizing overall profitability.
Current options:- Carbon rejection (coking, deasphalting)
Hydrogen addition (resid hydroprocessing) (needs additional
hydrogen)
These options leave behind undesired hydrogen-deficient materialrich in carbon, sulfur, metals etc.
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OTHER OPTIONS..
The ability to convert this unmarketablematerial to produce electricity, cleanlighter fuels and petrochemicals permitsthe refinery to increase its profitability
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The refiner can choose among three electric-
power-generation methods:
Circulating-fluidized beds (CFB)
Boilers with flue gas desulfurization (FGD) Integrated gasification combined cycle (IGCC)
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Primary factors affecting the selection for
power generation need balancing
- Environmental issues
- Efficiency
- Economics while preserving strategic
options for future investments.
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RESIDUE CONVERSION
GASIFICATION
Gasification
Power, hydrogen
Syn gas petro-chemicals
Offers an alternative to handle high sulfur and metalcontaining residues in a refinery with value addition
Alternative economically attractive option for many of the
problems associated with changing scenario in thepetroleum refining industry
Great advantage in co-generation and petro-chemicals viasyn gas
COMPARISON OF ELECTRICAL GENERATION OPTIONS
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COMPARISON OF ELECTRICAL GENERATION OPTIONS
CFB FGD IGCC
Sulfur-removalexperience
95% 95% +98%
Merchantable sulfur No No Yes
Oxygen/ nitrogenbyproduct No No Yes
Hydrogen
byproduct
Cost. $/kw
No
900
No
700
Yes
800-1,000
COMPARISON OF TYPICAL EMISSIONS, LB/MW-HR @
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, @
100% CAPACITYNatural gas
combinedcycle
Coke gasif.
Combined cycle
Coke
circulatingfluid bed
Coke
boiler FGD& SCR*
SO2 0.0 0.5 3.7 3.6
NOx 0.3 0.4 0.9 1,5
CO 0.2 0.3 1.5 NAVOC 0.02 0.07 0.08 NA
Particulates 0.05 0.07 0.2 0.2
CO2 820 1,930 2,170 2,120
Solid waste 0.00 9.1 350 190
*Fuel gas desulfurization and selective catalytic reduction.The solid wastes from acoke gasifier contain only the feed metals plus some carbon.
PETRO CHEMICALS FROM REFINERY
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PETRO-CHEMICALS FROM REFINERY
COKE
Valuable material for producing petro-chemicals
Excellent source for high purity acetylenewhich is a useful starting material for host of
petro-chemicals such as acrylonitrile,vinylchloride, acrylic monomer etc.
PETRO CHEMICALS FROM REFINERY COKE
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PETRO-CHEMICALS FROM REFINERY COKE
CRUDEOIL
REFINERY GASOLINE, DISTILLATE, ETC
REFINERY
CALCIUM
CARBIDE
PLANT
PETROCHEMICAL
PLANT
ELECTRIC
UTILITY
RES. & COMM. POWER
TO COMMUNITY
COKEACETYLENE
OR
CARBIDE
PETROCHEMICALPRODUCTS
POWER
CaCN 2HCNMgACRYLONITRILEVINYL CHLORIDE PLASTICSACRYLIC MONOMERACETYLENE BLACKCHLORINATED SOLVENTSACETALDEHYDE
ACETIC ACIDACETIC ANHYDRIDEACETYLENE CHEMICALSFROM REPPE CHEMISTRY
Figure -12: Fuel power relationship between refinery, utility plant, carbide plant, and petrochemical plant
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Impact of Diesel Quality
If only further sulfur reduction isinvolved, there is likely no impact onpetro-chemicals.
Summary:
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Summary:
More stringent gasoline specifications will change refiningand petrochemical synergies, as they will have an impacton refinery/ petrochemical interfaces.
Future diesel specifications are likely to have very little orno impact on refining and petrochemical integration.
Isomerization of light naphtha likely to play an importantrole.
Pyrolysis gasoline upgradation need to be relooked.
FCC, DCC and CPP will have major impact onpetrochemical refinery integration
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